Compositions stabilized with 1,4-disubstituted-7-azabicyclo (2.2.1) heptane-2,5 or 2, 6-dicarboxylic acid esters

ABSTRACT

Organic polymeric materials, especially polyolefins, which are subject to ultraviolet light degradation, are effectively stabilized with compounds having the formula   WHEREIN R1 is aryl, R2 is alkyl, benzyl or aryl, and R3 is alkyl.

United States Patent COMPOSITIONS STABILIZED WITHI,4-DISUBSTITUTED-7-AZABICYCLO (2.2.I) HEPTANE-2,5 OR 2. 6-DICARBOXYLICACID ESTERS Inventor: John F. Stephen, New City, N.Y.

Assignee:

US. Cl 260/458 N; 99/163; 252/50; 260/4585 S; 260/4585 B; 260/4585 P;260/4595 D; 260/4595 R; 260/4595 H;

Int. Cl. .i C(lSf 45/60; C08g 5l/6O Field of Search 4. 260/458 N. 45.85N; 99/l63; 252/50 References Cited FOREIGN PATENTS OR APPLICATIONS2/l964 United Kingdum [45] May 13, 1975 Primary Examiner-V. P. HokeAllorney, Agen! or Firm-Nest0r W. Shust {57] ABSTRACT Organic polymericmaterials, especially polyolefins, which are subject to ultravioletlight degradation are effectively stabilized with compounds having theformula C co R wherein R is aryl, R is ulkyL henzyl 0r aryl and R" isalkyl.

I3 Claims. N0 Drawings COMPOSITIONS STABILIZED WITHI,4-DISUBSTITUTED-7-AZABICYCLO (2.2.1) HEPTANE-2.5 OR 2,6-DICARBOXY LICACID ESTERS DETAILED DISCLOSURE This invention relates to compositionscomprising or ganic materials which are subject to ultraviolet lightdegradation stabilized with compounds having the formula co R wherein Ris phenyl or alkyl substituted phenyl,

R is phenyl, alkyl substituted phenyi, alkyl of i to 6 carbons. benzylor alkyl substituted benzyl and R" is alkyl group from 1 to 24 carbons.

In the preferred embodiment. R is phenyl; R is phenyl, benzyl or methyland most preferable phenyl or benzyl; and R is straight or branchedalkyl of l to l8 carbons and most preferably alkyl groups of 4 to 8carbons.

It is noted that in the above structure the group CO R is floating. Thatmeans that said group could be located at either the 5 or the 6position. lt is extremely difficult to determine the exact location ofsaid group, and often the product in fact may contain a mixture of the2,5- and 2.6- isomers. The mixture is most iikely when R or R groups aredissimilar, while a mixture is less likely when R and R are the same. itis the intention of this invention to cover both the 2,5 and the 2.6-compounds. the mixtures thereof and the compositions stabilized with the2,5- and 2.6 compounds and with mixtures thereof.

Esters of l.4-diphenyl-7azabicyelo[2.2.l lheptane- 2,5- or 2,6dicarboxylic acid can be prepared by reach ing 2,4-diphenyl-A-oxazolinone-S with an appropriate acrylate ester as described byHuisgen. Gottliardt and Bayer in Chem. Bet, 103, 2368 (1970). The2,4-diphenyl-N-oxazolinone-S can be obtained according to the procedureof Gotthardt, Huisgen and Bayer described in J. Amer. Chem. Soc., 92,4340 (1970).

Esters of l.4-diphenyl-Tazabicyclol2.2. l lheptane- 2,5- or2,6-dicarboxylic acid can also be obtained by reacting alkali metalsalts of l,4-diphenyl-7- azabicyclo[2.2. l ]heptane-2 5- or 2,6-dicarhoxylic acid with the appropriate alkyl halide in a dipolar aproticsolvent such as N,N-dimethylformamide. Suitable alkali metal saltsinclude the lithium, sodium and potassium salts. l.4diphenyl-7-azabicyclol2.2.l ]heptane-2,5- or 2,6-dicarboxylic acid canbe prepared by saponifying methyl l,4-diphenyblazabicyclol2.2.l-]heptane-2,5- or 2,6-dicarboxylate with aqueous ethanolic potassiumhydroxide. Dimethyl l,4-diphenyl-7- azabicyelolllllheptane-ILS or2,6-dicarboxylate can be obtained by the procedure of Huisgen. Gotthardt and Bayer, in Chem. Ber., MB, 2368 (1970).

Esters of lmethyl-4-phenyl and l-ben2yl-4-phenyl- 7-azabicyclol2.2.l]heptane'2,5- or 2.6-dicarboxyiic acids can be prepared by reacting2phenyl 4-methyl- N-oxazolinone-S and 2-phenyl-4-benzyl-A oxazolinone-S,respectively, with the appropriate acrylate ester.2-Phenyl-4methyLY-oxazolinone-5 can be prepared according to theprocedure described by Got thardt, Huisgen and Bayer in J. Amer. chem.Soc. 92. 4340 (1970). 2phenyl-4-benzyl-A mxazolinone-fi can be preparedas described by Carter in Org. Reactions. 3. 205.

The esters of l-methyl-4-phenyl and l-benzyl-4- phenyl-7-a7abicyclol2.2,l lheptanelfior 21 dicarboxylic acids can also be prepared byalkylating the alkali metal salts of the appropriate acid with theappropriate alkyl halide in a dipolar aprotic solvent such as NN-dirnethylformamide. Suitable alkali metal salts are the lithium.sodium and potassium salts. The required acids can be prepared bysaponifying the methyl or ethyl ester olthe corresponding acids.

Illustrative examples of the stabilizers of this inven tion are:

A. Dimethyl i.J-diphenyl7-aiahicyclol lll lhcptanc- 2.5- orZb-dicarboxylatc B. Diethyl lmetliyl4'phenylJ-azahicyclol2.2.l ]heptane-2.5- or lo-dicarhoxylalc C. Di-nbutyl l-methyl4-phenyl7-azabicyclo[2.2.1

lheptane-Zfi or 2.(Hliearhoxylate D. Di-n-butyll'bcmyllphenyl7-azabicyclo[2.2.l

iheptane-Zfior lodicarhoxylate E. Di-n-butyll.4diphenyl-7-arabicyclol2.2.1lheptame-2.5 or lh-dicarboxylate F.Di-n-octyl l-methyl--l-phenyl-7-azabicyclol2,2.l-

iheptane--Z,5- or 2.(i-dicarhoxylati:

G. Di-moctyl l.4-diphenyl-7-a/ahicyclol2.2.1]hep tune-2.5 orZjvtliearboxylate H. Di-(l-ethylhewli ambicycloll 2.1I-hepatane-lidicarboxylate l. Di-n-octyl l-hemiyl-4-phenyl-7-azabieycl-{2.2.1 lheptanefljor lo-dicarboxylate .l. Di-(Lethylhexyl)i.4-diphenyl-7-azabicyclol2.2.1

heptane-2,5- or 2,(1-dic: irboxylate K. Di-(Z-ethylhexyi)l-ben2yl-4-phenyl-7- azabicyclollll j-heptane-Zfi or lh-dicarboxylate L.Dim-dodecyl l.44!iphenyl-7-azabicyclol2.2.] lhcptane-2,5- or 2o-dicarboxylate M. Di-n--docedyl I -methyl 4-phenyl-7- azabicyclolllll-heptane2.5 or 2.(1-dicarboxylate N. Dim-dodecyl l-ben2yl-4pheny|-7-azabicyclol2.2.i l-heptane-Zfior 2.6-dicarboxylate O. Di-noctadeeyll,4-diphenyl-laxabicyelol2.2.l-

lheptane-2.5- or lo-dicarboxylate P. Di-n-octadecyl l-methyl-4-phenyl-7-azabicyclolZll]-heptane-2.5- or Zjvdiearboxylate Q Di n-octadecyll-benzyl-4-phenyl 7- azabicyelollll l-heptane-2 5- or Zb-dicarboxylateThe preparation of the compounds employed as stabilizers in thisinvention is further illustrated in the following examples.

EXAMPLE I l,4-DiphenylTAzabicyclo {2.21} heptane-2,S or 2,6-DicarboxylicAcid under reflux for 16 hours. After clarification by filtration overfilter aid the mixture was acidified with 33.1 ml of 37.6 percenthydrochloric acid. The precipitated solid was collected by filtration.and the filtrate was evaporated to dryness under reduced pressure togive a semi-solid residue. The solid material was washed thoroughly withwater to give 14.8 g. of a white solid. m.p. SAW-243 dcc. The semi-solidresidue above t as extracted with boiling methanol. The insoluble solidwas filtered off and washed with water. methanol and then ether to givea second crop oi 19.4 g of white solid. mp. 23423o dec. The combinedyield (34.2 g) was 60 percent. No suitable solvent could be found torecrystallize this highly insoluble amino acid. An analytical sampleprepared by reprecipitation from sodium hydroxide solution had mp.PAP-243 dec.

EXAMPLE 2 Di n-Butyl l.4-Dipheny'l-T Azabicyclo {2.2.11 heptane-Zj orlb-Dicarboxylate l.4-diphenyl-T -azabicyclo {2.2.11 heptane-2.5 orZb-dicarboxylic acid (5.06 g. 0.015 mole) was dissolved in N KOH inmethanol solution 130 ml. 0.03 mole l. The solution was evaporated todryness under reduced pressure and the dipotassium salt thus obtainedwas heated at 5060/0.0l mm for several hours. The potassium salt wassuspended in 150 ml of dry N.N-dimethylformamide, l-bromobutane (4.11 g.0.03 mole) was added. and the mixture was stirred and heated at 90-95for hours. The solvent was evaporated under reduced pressure and theresidue was dissolved in ether. The ether solution was filtered frominsoluble material and then evaporated under reduced pressure to give6.3 g of a yellow oil. Chromatography of this material on 160 g ofsilica gel using benzenechlorotorrn 1 1:1 1 as solvent gave the purediester 5.4 g (80 percent] as a pale yellow oil.

EXAMPLE 3 Diethyl l-Methy'lA-PhenylT-Azabicyclo [2.2.1] heptane3.5 orlb-Dicarboxylate lphenyl-4-methyl-.V-oxazolinone-5 (10.0 g. 0057i mole)was dissoh ed in 50 ml of ethyl acrylate and the mixture heated underreflux for 20 hours. Excess ethyl acrylate was evaporated under reducedpressure and the residue was dissolved in ether. The ether solution wassaturated with hydrogen chloride gas. Water was added to dissohe theoily hydrochloride salt which had separated. The ether layer wasseparated and discarded. The aqueous solution was washed several timeswith ether and then the pH was adjusted to 11 by addition of IN sodiumhydroxide solution. The oil which was separated was extracted witheither. Evaporation of the dried (M1 ether solution and distillation ofthe resulting oil in vacuo gave the title compound 3.8 g (10 percent) asthe fraction bp. l3tll 3Z/'(l.01 mm.

The compounds of this invention are stabilizers of organic materialnormally subject to thermal. oxidative or actinic light deterioration.Materials which are thus sta bilized include synthetic organic polymericsubstances including homopolymers. copolymers. and mixtures thereof.such as vinyl resins formed from the polymer ization of vinyl halides orfrom the copolymerization of vinyl halides with unsaturatedpolymerizable com pounds. cg. vinyl esters. mB-unsaturated acids.afi-unsaturated esters. mfl-unsaturated ketones.

a.Bunsaturated aldehydes and unsaturated hydrocarbons such as butadienesand styrene. poly-a-olefins such high and low density polyethylene.cross-linked polyethylene. polyporpylene. polyl-l-methylpentene-l andthe like. including copolymers of oz-olefins: such as ethylene-propylenecopolymers. and the like; dienes such as polybutadiene. polyisoprene.and the like. including copolymers with other monomers; polyurethanessuch as are prepared from polyols and organic polyisocyanates. andpolyamides such as polyhexamethylene adipamide and polycaprolactam;polyesters such as polyethylene terephthalates; polycarbonates such asthose prepared from bisphenol-A and phosgene; polyacetals such aspolyethylene terephthalate polyacetal; polystyrene. polyethyleneoxide'.polyacrylics such as polyacry'lonitrile; polypheny'leneoxides such asthose prepared from 2.6-dimethylphenol and the like; and copolymers suchas those of polystyrene con taining copolymers of butadiene and styreneand those formed by the copolymerization of acrylonitrile. butadieneandlor styrene Other materials which can be stabilized by the compoundsof the present invention include lucricating oil of the aliphatic estertype. ie. di (1.Z-ethylenc)- azelate. pentaery thritol tetracaproate.and the like: animal and vegetable deri ed oils. e.g.. linseed oil. fat.tallow. lard. peanut oil. cod liver oil. castor oil. palm oil. corn oil.cottonseed oil. and the like: hydrocarbon materials such as gasoline.mineral oil. fuel oil. drying oil. cutting fluids. waxes. resins. andthe like. salts of fatty acids such as soaps and the like; and alkylenegylcols. e.g.. B methoxyethylenegly'col. methoxytriethy'leneglvcol.triethylene glycol. octaethyleneglycol. dibutyleneglycol.dipropyleneglycol and the like.

The compounds of this invention are particularly useful as L'\' lightstabilizers. especially for the protection of polyolefins. for instance.polyethylene. polypropylene. polytbutened polytpentene-l l. poly (3-methylbutene-l l. poly(-l-methylpentene-ll. various ethylene-propylenecopolymers and the like.

In general. the stabilizers of this invention are employed from about0.01 to about 5 percent by weight of the stabilized composition.although this will vary with the particular substrate and application.An advantageous range is from about 0.05 to about 2 percent andespecially 0.1 to about 1 percent.

For addition to polymeric substrates. the stabilizers can be blendedbefore polymerization or after polymerization. during the usualprocessing operations. for example. by hot-milling. the composition thenbeing extruded. pressed. blow molded or the like into films. fibers.filaments. hollow spheres and the like. The heat stabilizing propertiesot these compounds may advantageously stabilize the polymer againstdegradation during such processing at the high temperature generallyencountered. The stabilizers can also be disolved in suitable solventsand sprayed on the surface of films. fabrics. filaments or the like toprovide effecthe stabilization. Where the polymer is prepared from aliquid monomer as in the case of styrene. the stabilizer may bedispersed or dissolved in the monomer prior to polymerization or curing.

These compounds can also be used in combination with other additivessuch as antioxidants. sulfurcontaining esters such asdistearyl-B'thiodipropionate (DSTDPl. dilauryl-B-thiodipropionate(DLTDP) in an amount of from 0.01 to 1 percent by weight of the or'ganic material. and the like. pourpoint depressants. corrosion and rustinhibitors. dispersing agents. demul sifiers. antifoaming agents.fillers such as glass or other fibers. carbon black. accelerators andthe other chemi cals used in rubber compounding, plasticizers, colorstabilizers. diand tri-alkyl and alkylphenylphosphites, heatstabilizers. ultraviolet light stabilizers, antiozonants. dyes.pigments. metal chelating agents. dyesites and the like. Oftencombinations such as these. particu larly the sulfur containing esters.the phosphites and/or the ultraviolet light stabilizers will producesuperior results in certain applications to those expected by theproperties of the individual components.

The following formula represents co-stabilizers which are in certaininstances very useful in combination with the stabilizers of thisinvention:

wherein R is an alkyl group having from 6 to 24 carbon atoms; and n isan integer from I to 6. Especially useful compounds of this type aredilauryl-B-thiodipropionate and distearyl-B-thiodipropionate. The abovecostabilizers are used in the amount of from 0.0] to 2 percent by weightof the organic material, and preferably from 0.] to 1 percent.

Although the compounds of this invention may to some degree also beeffective as thermal stabilizers. if the processing of the polymer iscarried out at high temperatures it is advantageous to incorporateadditional antioxidants.

ln most applications. it is desirable to incorporate into the resincomposition. sufficient thermal antioxidants to protect the plasticagainst thermal and oxidative degradation. The amount of antioxidantrequired will be comparable to that of the actinic stabilizer. Namely.from about 0.005 percent to percent and preferably from 0.0] percent to2 percent by weight Representative of such antioxidants are phosphiteesters, such as triphenylphosphite and dibutylphosphite and alkylarylphosphites such as dibutylphcnylphosphite. and the like.

The best results have been obtained with the pre ferred class of thermalantioxidants, the hindered phenols. These compounds have been found toprovide the best thermal stabilization with the least discoloration inthe compositions of the invention. Among these phenolic antioxidants areincluded the following;

di-n-octadccyll 3-5-butyl-4-hydroxy-5-methylbenzyljmalonate2.o-di-t-butylphenol 2.2'-mcthylene-bis(6 t-butyl-4-rnctl'lylphenol)2.6di-t butylhydroquinoneoctadecyl-(3.5-di-tbutyl-4hydroxybcn7ylthio)acctatcl.l.3tris(3-t-butyl-6-methyl-4-hydroxyphcnyl)- butane2.4-bis-(3,5-di-t-butyl-4-hydroxyphenoxy)-6-(noctylthio)-l.3.5-triazine2.4-bis-(4 hydroxy-3.5-di-t-butylphenoxy)-6-(n octylthioethylthio)- l .3.5triazinc2.4-bis-(n-octylthio)6-(3.5-di-t-butyl-4-hydroxyanilino)-l,3.5-triazine2.4.6-tris-(4-hydroxy3.S-di-t-butylphenoxy)- l .3.5- triazinen-octadecyl-B-(3.5-di-t-butyl-4-hydroxyphenyl) propionate noctadecyl3.5-di-t'butyl4-hydroxybenzoate 2-(n-octylthio)ethyl-3.5-di-tbutyl-4hydroxybenzoate stearamido N.N bis- {ethylene 3-(3.5-di-t-butyl-4-hydroxyphenyl)propionatel l.2-propylene glycol hydroxyphenyl)propionatelpentaerythritol tetrakis-{3-( 3.5di-t-butyl-4-hydroxyphenyl )propionate}dioctadecyl-3.5-di-t-butyl-4-hydroxybenzylphosphonatedi-n-octadecyLl-(3.5-dit-butyl-4-hydroxyphenyl)- ethanephosphonate Theabove phenolic hydrocarbon stabilizers are known and many arecommercially available.

The above antioxidants have been listed only for the purpose ofillustration and it is important to note that any other antioxidant canbe employed with similar improved results. The above exemplifiedantioxidants and other related antioxidants which are incorporatedherein by reference. are disclosed in greater detail in the followingpatents: Netherlands Patent specification 67/1] 19. issued Feb. 19.1968; Netherlands Patent specification 68/03498 issued Sept. 18. 1968:US. Pat. Nos. 3.255.19l; 3.330.859. 3.644.482. 3.28l.505; 3.531.483,3.285.855. 3.364.250; 3.368.997; 3.357.944 and 3.758.549.

EXAMPLE 4 Artificial Light Exposure Test Deterioration of most polymerscaused by ultraviolet light is so slow at ambient temperatures. even inthe absence of stabilizers. that testing of the effects of stabilizersgenerally must be conducted either at higher temperatures or in anaccelerated artificial light exposure device in order to yield resultsin a convenient period of time. The tests conducted on polymers using anaritficial light exposure device is described below:

a. Sample Preparation 5 mil Film Unstabilized polypropylene powder(Hercules Profax 6501) is thoroughly blended with the indicated amountsof additives. The blended material is then milled on a two roll mill for5 minutes at 182C. The milled sheet is then compression molded at 220Cinto 5 mil thick film under a pressure of psi and water cooled in thepress.

b. Testing Method This test is conducted in a FS/BL unit. basically ofthe American Cyan-amid design. which consists of 40 tubes of alternatingfluorescent sunlamps and black lights (20 of each). The 5 mil samplefilm which are mounted on 3 X 2 IR card holders with A X 1 windows andare placed on a rotating drum 2 inches from the bulbs in the FS/BL unit.The time in hours is noted for the development of 05 carbonyl ahsorhanceunits are determined on an Infra red Spectrophotometer. The developmentof car oonyl functional groups in the polymer is propor tional to theamount of degradation caused by the ultraviolet light exposure.

The test results reported below were obtained according to theprocedures described above. The amounts of the additives are expressedin weight per cent based on the weight of the polymer.

TABLE 1 l ight Sta'nih/utlon ol' Polypropylene Time in Hours to 0.5Carbonyl Ahsorbnncc l nrts htiilnluci iormu A Formul. B

i C mpound A 440 860 1 Compound B 175 810 1 Comp und D mo W55 4 ompoundl 13 0 (-uupound U 5540 ltfi'it ti Compound l Mill ih lti 7 Compound Khi5 I740 ti Compound l 555 H35 1 Compound U 470 i000 l0 Nntic 210 555 cIt I hydroxy5 nrethylphcnyl .l-benzotriazole,

EXAMPLE 5 High impact polystyrene resin containing elastomer tiehutadiene-styrencl is stabilized against loss of elongation propertiesdue to exposure to ultraviolet light by incorporation of 0.3 percent byweight of di-n butyl imethyll4-phenyl-7-azabicyclo- [2.3.1 Zlheptnne5-or 2.6-dicarhoxylate.

The unstahilimd resin is dissolved in chloroform and the stabilirer thenadded, after which the mixture is cast on a glass plate and the solventevaporated to yield a uniform film which upon drying is removed and Cutup. and then pressed for 7 minutes at a temperature of 263C and apressure of 2,000 pounds per square inch into a sheet ol uniformthickness mil)v The sheets are then cut into strips approximately 4 X0.5 inches. A portion of these strips is then measured for percent ofelongation in the lnstron Tensile Testing Apparatus (lnstron EngineeringCorporation, Quincy, Massachusetts). The remaining portions of thestrips are placed in an FS/BL chamber according to Example 7(8) exceptthat the samples are mounted and white cardboard stock and the time to50 percent reduction in elongation is measured. The stabilizedpolystyrene resin retains its elongation property longer than theunstabilized resin.

EXAMPLE 6 Unstabilized linear polyethylene is solvent blended inmethylene chloride with 0.5 percent by weight of the substrate ofdi-n-octyl lmcthyl-4-phenyl-7- axahicycloi 1.2.1 iheptanc 2 5- or2,fidicarboxylate and then vacuum dried. The resin is then extrusioncompounded on a 1 inch 24/l L/D extruder melt temperature 450F. (232C)and pressed for 7 minutes at a temperature of 163C and a pressure of1000 psi into a sheet of uniform thickness of [00 mil. The sheets arethen cut into plaques of 2 inch X 2 inch. The plaques are then exposedin a FS/Bl. exposure device and color measurements made periodicallyusing a Hunter Color Difference Meter Model D25. Polyethylene stabilizedwith the above compound is found to be much more stable than theunstahilized polyethylene or the polyethylene stabilized only with anantioxidant. is mixed for 5 minutes after which it is cooled andcompression molded at 125C into 5 X 0.025 inch plaques,

The plaques are exposed to a xenon arc weatherometcr and the colormeasurement (L-h) is made after 45, I25 and 290 hours. The samplesstabilized with the above compound are found to be much more lightstable than the unstahilized samples.

EXAMPLE 7 A quantity of SBR emulsion containing g of rubher I500 ml of20 percent SBR obtained from Texas U.S., Synpol 1500i previously storedunder nitrogen, is placed in a beaker and stirred vigorously. The pH ofthe emulsion is adjusted to 10.5 with a 0.5N NaOH solution.

To the emulsion is added 50 ml of 25 percent NaCl solution. A 6 percentNaCl solution adjusted with bydrochloric acid to a pH [.5 is added in athin stream with vigorous stirring. When pH 6.5 is reached. the rubherbegins to coagulate and the addition is slowed down in order to maintainuniform agitation. The addition of the acidic 6 percent NaCl solution isterminated when a pH 3.5 is reached. The coagulated crumb-rubber slurryat pH 3.5 is stirred for /2 hour.

The coagulated rubber is isolated by filtration through cheese cloth andrinsed with distilled water. After three subsequent washings with freshdistilled water, the coagulated rubber is dried, first at 25 mm Hg andfinally to constant weight under high vacuum 1 mm) at 4045C.

The dried rubber [.25 g) is heated under nitrogen at C in a Brabendermixer and to this is added with mixing 0.5 percent of di-(Z-ethylhexylll-methyl-4- phenyl-7-azabicyclol2.2.l i-heptane-Z S- or 2,6-dicarboxylate. The composition EXAMPLE 8 To 50 g of poiyacetai resincontaining 0.] percent of an acid scavenger, dicyandiamide, is added 0.2percent by weight of di-n-octyl lbenZylA-phenyl-7-azabicyclo- [1il.l]heptane-2,5- or 2,6-dicarboxylate and milled for 7 minutes at 200C in aBrabender Plasti-recorder. The milled formulation is subsequentlypressed into a 40 mil sheet at 215C at 350 psi for 90 seconds thencooled quickly in a cold press at 350 psi. The stabilized sheets arethen remolded for 2 minutes at Contact pressure and for 3 minutes at 300psi at 215C to give plaques 1 5% inch X 2 A inch X 125 mil. Thereafter,the testing procedure of Example 9 is followed to determine the lightstability of the samples. The stabilized samples are found to be muchmore stable than the unstabilized samples.

EXAMPLE 9 Unstabilized thoroughly dried polyethylene tetephthalate chipsare dry blended with [.0 percent of di-ndodecyll-methyL4-phenyl-7-azabicyclo {2.2.1 heptane-2,5- or 2,6-dicarboxylate.60/10 denier multifilament is melt spun at a melt temperature of 290C.The oriented fiber is wound on white cards and exposed in a Xenon ArcFadeorneter. Color measurements are made periodically with a HunterColor Difference Meter Model D25. The stabilized samples are found to bemuch more light stable than the unstabil ized samples.

What is claimed is:

l. A composition of matter comprising an organic material normallysubject to deterioration stabilized with (a) 0.01 to 5 percent ofastabilizer having the formula wherein R is phenyl, R is phenyl, benzylor lower alkyl, and R is alkyl from 1 to 24 carbons, (b) to percent of aphenolic antioxidant and (c) O to 5 percent of a thio co-stabilizer.

2. A composition of claim 1 wherein R is phenyl, benzyl or methyl and Ris alkyl having 4 to 8 carbons. 3. A composition ofclaim I wherein (b)the phenolic antioxidant is selected from di-moctadecyl3,5-di-tertbuty]-4-hydroxybenzylphosphonate,di-n-octadecyla,a'bis(3-butyl-4hydroxy-5-methylbenzyl)malonate and2,4-bis(4-hydroxy-3,S-di-tert-butylphenoxy)-6-(noctylthioethylthio)-1,3,5triazine,and (c) the thio co stabilizer is selected fromdilauryl-B-thiodipropionate and distearyl-B-thiodipropionate.

4. A composition of claim 3 wherein the organic material is polyolefin.

5. A composition of claim 4 wherein the polyolelin is polypropylene.

6. A composition of claim 5 wherein thc stabilizer is wherein R isphenyl,

R is phenyl, benzyl or methyl,

R is alkyl having from 4 to 8 carbons.

7. A composition of claim 6 containingdi-noctadecyl(3,5-di-tert-butyl-4hydroxybenzyl phosphonate and2(2-hydroxy 3',5'-di-tert-butylphenyl)-5 chlorobenzotriazole.

8. A composition of claim 7 wherein the stabilizer is di n-butyll,4-diphenyl-7-azabicyclol2.2.l lheptane- 2,5- or 2,6-dicarboxylate.

9. The composition of claim 7, wherein the stabilizer isdi-(Z-ethylhexyl) l.4-diphenylJ-azabicyclo [2.2.1] heptane-2,5-or2.6-dicarboxylate.

10. The composition of claim 7 wherein the stabilizer is di-n-butyll-benzyl-4-phenyl-7-azabicyclo [2.2.11 heptane-2,5-or 2,6-dicarboxylate.

11. The composition of claim 7, wherein the stabilizer isdi-(2-ethylhexyl) l-benzylQ-phenyl-T azabicyclo [2.2.1] heptane-2,5 0r2,6-dicarhoxylate.

12. The composition of claim 7, wherein the stabilizer is di-n-butyll,4-diphenyl-7-azabicyclo [212.1] heptane-2,5- or 2,6- dicarboxylate.

13. The composition of claim 7 wherein the stabilizer is dinoctyll,4-diphenyl-7azabicyclol2.2.l ]heptane- 2,5- or 2,6- dicarboxylate.

1. A COMPOSITION OF MATTER COMPRISING AN ORGANIC MATERIAL NORMALLYSUBJECT TO DETERIORATION STABILIZED WITH (A) 0.01 TO 5 PERCENT OF ASTABILIZER HAVING THE FORMULA
 2. A composition of claim 1 wherein R2 isphenyl, benzyl or methyl and R3 is alkyl having 4 to 8 carbons.
 3. Acomposition of claim 1 wherein (b) the phenolic antioxidant is selectedfrom di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate,di-n-octadecyl- Alpha , Alpha''-bis(3-butyl-4-hydroxy-5-methylbenzyl)malonate and2,4-bis(4-hydroxy-3,5-di-tert-butylphenoxy)-6-(n-octylthioethylthio)-1,3,5-triazine, and (c)the thio co-stabilizer is selected from dilauryl- Beta -thiodipropionateand distearyl- Beta -thiodipropionate.
 4. A composition of claim 3wherein the organic material is polyolefin.
 5. A composition of claim 4wherein the polyolefin is polypropylene.
 6. A composition of claim 5wherein the stabilizer is
 7. A composition of claim 6 containingdi-n-octadecyl(3,5-di-tert-butyl-4-hydroxybenzyl phosphonate and2(2''-hydroxy-3'',5''-di-tert-butylphenyl)-5-chlorobenzotriazole.
 8. Acomposition of claim 7 wherein the stabilizer is di-n-butyl1,4-diphenyl-7-azabicyclo(2.2.1)heptane-2,5- or 2,6-dicarboxylate. 9.The composition of claim 7, wherein the stabilizer is di-(2-ethylhexyl)1,4-diphenyl-7-azabicyclo (2.2.1) heptane-2,5-or 2,6-dicarboxylate. 10.The composition of claim 7 wherein the stabilizer is di-n-butyl1-benzyl-4-phenyl-7-azabicyclo (2.2.1) heptane-2,5-or 2,6-dicarboxylate.11. The composition of claim 7, wherein the stabilizer isdi-(2-ethylhexyl) 1-benzyl-2-phenyl-7-azabicyclo (2.2.1) heptane-2,5-or2,6-dicarboxylate.
 12. The composition of claim 7, wherein thestabilizer is di-n-butyl 1,4-diphenyl-7-azabicyclo (2.2.1) heptane-2,5-or 2,6-dicarboxylate.
 13. The composition of claim 7 wherein thestabilizer is di-n-octyl 1,4-diphenyl-7-azabicyclo(2.2.1)heptane-2,5- or2,6-dicarboxylate.